Pioline made his decisive break in the first game of the third set and comfortably held off the 1997 French Open champion's efforts to save the tie, winning in 1hr 51min.
He clinched the match on his second match point in typical fashion, firing in a thundering service and following it up with a smart forehand volley.
Pioline did not drop a set in his two singles matches and outplayed Kuerten, ranked fifth in the world. "In such an atmosphere, you can only win. I think I played a very good match, almost perfect," Pioline said after his victory on the fast, synthetic surface of the Pau sports hall.
The surface undermined the chances of the Brazilian clay court specialists although Kuerten took the opening singles against Sebastien Grosjean on Friday. Brazil's No 1 needed five sets in a match lasting nearly five hours to beat Grosjean and he also played in Saturday's doubles.
By the time Kuerten faced Pioline, he had spent almost seven hours on court to the Frenchman's 1hr 50min, the time it took Pioline to beat Fernando Meligeni on Friday.
Kuerten and Jaime Oncins lost a Davis Cup match for the first time against Fabrice Santoro and Olivier Delaitre in Saturday's doubles.
France, who have won the trophy twice in the 1990s, are at home again in the semi-final against Belgium in September and will start as clear favourites although Belgium relegated them from the World Group only two years ago.
Both times France have reached the semi-finals since 1991, they went on to lift the trophy.
Belgium qualified for the semi-finals for the first time in the modern era yesterday when 18-year-old Xavier Malisse struggled past Switzerland's Roger Federer in the first of the reverse singles.
Malisse's 4-6, 6-3, 7-5, 7-6 win over the 17-year-old Federer gave Belgium a 3-1 lead. The match lasted three hours and 10 minutes and left both players on the verge of exhaustion.Reuse content